EP0085776B1 - Novel composition for polyurethane resins - Google Patents

Novel composition for polyurethane resins Download PDF

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Publication number
EP0085776B1
EP0085776B1 EP82111619A EP82111619A EP0085776B1 EP 0085776 B1 EP0085776 B1 EP 0085776B1 EP 82111619 A EP82111619 A EP 82111619A EP 82111619 A EP82111619 A EP 82111619A EP 0085776 B1 EP0085776 B1 EP 0085776B1
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EP
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Prior art keywords
polyol
group
composition
isocyanate
component
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EP82111619A
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German (de)
English (en)
French (fr)
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EP0085776A1 (en
Inventor
Yoshio Kamatani
Michio Tanaka
Kyuya Yamazaki
Kenichi Nishino
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Takeda Pharmaceutical Co Ltd
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Takeda Chemical Industries Ltd
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    • A—HUMAN NECESSITIES
    • A63—SPORTS; GAMES; AMUSEMENTS
    • A63B—APPARATUS FOR PHYSICAL TRAINING, GYMNASTICS, SWIMMING, CLIMBING, OR FENCING; BALL GAMES; TRAINING EQUIPMENT
    • A63B41/00—Hollow inflatable balls
    • A63B41/08—Ball covers; Closures therefor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/50—Polyethers having heteroatoms other than oxygen
    • C08G18/5021—Polyethers having heteroatoms other than oxygen having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6266—Polymers of amides or imides from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6283—Polymers of nitrogen containing compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/64—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63
    • C08G18/6415—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having nitrogen
    • C08G18/643—Reaction products of epoxy resins with at least equivalent amounts of amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/701—Compounds forming isocyanates or isothiocyanates in situ
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/7875—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring
    • C08G18/7887—Nitrogen containing heterocyclic rings having at least one nitrogen atom in the ring having two nitrogen atoms in the ring

Definitions

  • This invention relates to a novel composition for polyurethane resins. More particularly, it relates to a composition for polyurethane resins which contains an isocyanate component having oxadiazinetrione ring and a polyol component having at least one of a tertiary amino group, a quaternary ammonium group and a carboxylate salt group in the molecule.
  • polyurethane resins have been used as, for example, coatings, adhesives and elastomers for various substrates such as woods, metals, roofing tiles, concrete, plastics, rubbers, papers, floor covering materials, water proof materials, sealing materials, etc. because they are superior to other synthetic resins in chemical resistance, stain resistance, adhesiveness, gloss, wear resistance, physical properties, weathering resistance, etc.
  • compositions for polyurethane resins are classified as one-package type and multi-package type such as two-package type.
  • the two-package type compositions usually comprise a polyol component which is a main component and a polyfunctional polyisocyanate component which is a curing agent.
  • a curing agent has to be stored in a condition free of moisture, because of its instability to moisture.
  • this curing agent ordinarily used are derivatives such as polyisocyanates having urethane, urea or biuret bond obtained by reaction of a diisocyanate with a polyol, water, amine, etc. and polyisocyanates having isocyanurate ring obtained by trimerization of a diisocyanate in the presence of catalysts.
  • polyurethane plastics prepared by reacting polyisocyanates having a 1,3,5-oxadiazine-2,4,6-trione ring and with an organic compound containing active hydrogen which is reactive with an isocyanate group.
  • organic compounds containing active hydrogen are mentioned among others polyester polyols and polyether polyols.
  • Triethanolamine is mentioned as a starting material for preparing polyester polyols, but polyester polyols having a tertiary amino group are not specifically mentioned.
  • ammonia and several amines such as diethanolamine and triethanolamine are mentioned as initiators for preparing polyether polyols.
  • Zinc octoate is mentioned as a catalyst which can catalyse only the reaction of a hydroxyl group with an isocyanate group to form a urethane group but not the cleavage reaction of a hydroxyl group with an oxadiazinetrione ring to form an allophanate group.
  • the EP-A-0 043 651 an older application which is not prepublished, relates to polyisocyanates having oxadiazinetrione rings obtained by reacting a bis(isocyanatomethyl)cyclohexane, an oligomer thereof, an adduct thereof or a mixture of them with carbon dioxide and to the use of said polyisocyanates in the production of polyurethanes by reaction with active hydrogen compounds.
  • active hydrogen compounds are mentioned polyols such as acrylic polyol and polyester polyol.
  • composition comprising a curing agent mentioned above and a polyol component having at least one of a tertiary amino group, a quaternary ammonium group and a carboxylate salt group in the molecule exhibits excellent curability, film and adhesive performance and physical properties after cured.
  • this invention has been accomplished.
  • This invention relates to a composition for polyurethane resins which comprises an isocyanate component having oxadiazinetrione ring and a polyol component having, in the molecule, at least one of a tertiary amino group, a quaternary ammonium group and carboxylate salt group, wherein the amount of the tertiary amino group, the quaternary ammonium group and/or the carboxylate salt group in the molecule of the polyol component is such that the proportion of nitrogen of the tertiary amino or quaternary ammonium group or that of carbonyloxy group of the carboxylate salt group to the whole composition is 0,0001 to 10% by weight.
  • the isocyanate component having oxadiazinetrione ring used in this invention means a compound having two reactive groups, i.e., oxadiazinetrione ring and isocyanate group together in one molecule.
  • Such compound can be prepared by known method, specifically, by the reaction of an isocyanate with carbon dioxide.
  • the isocyanates include aliphatic, alicyclic and aromatic-aliphatic polyisocyanates, e.g., tetramethylene diisocyanate, hexamethylene diisocyanate, w,w'-diisocyanatodipropyl ether, 2,6-diisocyanatocaproic acid ester, 1,6,11-triisocyanatoundecane, bis(isocyanatomethyl)cyclohexane, bis(isocyanatoethyl)cyclohexane, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, bis-(4-isocyanatocyclohexyl)methane, xylylene diisocyanate and bis(2-isocyanatoethyl)benzene.
  • aliphatic, alicyclic and aromatic-aliphatic polyisocyanates e.g., tetram
  • polyisocyanates may be used alone or as a mixture thereof. Furthermore, these polyisocyanates may be used as mixtures with monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, w-chlorohexyl isocyanate, cyclohexyl isocyanate, cyclohexylmethyl isocyanate, benzyl isocyanate or phenylethyl isocyanate.
  • monoisocyanates such as methyl isocyanate, ethyl isocyanate, n-butyl isocyanate, w-chlorohexyl isocyanate, cyclohexyl isocyanate, cyclohexylmethyl isocyanate, benzyl isocyanate or phenylethyl isocyanate.
  • the reaction of the isocyanate with carbon dioxide is carried out in the presence of a catalyst.
  • a catalyst tertiary phosphines, arsenic compounds and hydroquinones may be used and the tertiary phosphines are especially effective.
  • the reaction product may be used, as it is, as the isocyanate component of this invention, but usually various compounds are preferably added thereto for termination of the reaction when predetermined reaction rate has been attained and for stable storage of the product.
  • reaction terminators and stabilizers include alkylating agents, acylating agents, acids, ester derivatives, phenols, peroxides, sulfur, polysulfides, metal sulfides, halogens, etc.
  • the isocyanate component having oxadiazinetrione ring to which an additive selected from peroxides, sulfur, polysulfides, metal sulfides and halogens is added is preferred because the reaction of oxadiazinetrione ring and isocyanate with hydroxyl group of polyol component smoothly proceeds.
  • adducts having terminal NCO group may also be used as the polyisocyanate.
  • Such adducts can be obtained by reacting polyisocyanates with polyol compounds (e.g., ethylene glycol, propylene glycol, 1,4-butanediol, glycerine, trimethylolpropane, polyether polyol, polyester polyol, acrylic polyol or epoxy polyol) or polyamine compounds (e.g., ethylenediamine, hexamethylenediamine, phenylenediamine, polyether polyamine or polyamide polyamine) in an excess ratio of NCO group to active hydrogen of the polyol or polyamine compounds.
  • Polyisocyanates, NCO of which is partially blocked with a blocking agent and those having partially dimerized or trimerized NCO groups may also be used as the polyisocyanates.
  • the isocyanate component adducts may also be used as the isocyanate component adducts, blocked derivatives and polymerized derivatives of the isocyanate having oxadiazinetrione ring obtained by reaction of polyisocyanate with carbon dioxide.
  • the addition reaction, blocking reaction of polymerization reaction may be carried out simultaneously with the reaction of preparing the oxadiazinetrione ring.
  • isocyanate components having oxadiazinetrione ring enumerated above those which are derived from hexamethylene diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane or bis(isocyanatomethyl)cyclohexane provide compositions especially excellent in physical properties and curability.
  • the isocyanate component having oxadiazinetrione ring employable in this invention is one having an average functionality of preferably 2 to 10 which is the sum of oxadiazinetrione ring and isocyanate group in one molecule.
  • the functionality is optionally determined depending on functionality, OH value and molecular weight of the polyol component, molecular structure of curing agents and physical properties of cured resins.
  • isocyanate component contains unreacted isocyanate monomers, low functional substances, etc. and, therefore, is unsuitable to use as it is, it is also possible to remove the monomers, low functional substances, etc. by appropriate methods such as distillation, extraction, crystallization, etc.
  • isocyanate component having oxadiazinetrione ring can be used as a curing agent as it is.
  • these isocyanate components may be used in such forms as suitable for use by diluting them with organic solvents, thinners, etc.
  • polyol component having in the molecule at least one of a tertiary amino group, a quaternary ammonium group and a carboxylate salt group which can be used in this invention, mention may be made of a compound containing at least two hydroxyl groups and having a molecular weight of 100 to 100,000, preferably 100 to 50,000. More preferred is a polyol having 2 to 50 hydroxyl groups in the molecule and having a molecular weight of 100 to 30,000.
  • polyester polyols there may be used polyester polyols, polyether polyols, polyether-ester polyols, polyester-amide polyols, acrylic polyols, polyurethane polyol, epoxy polyols, epoxy-modified polyols, oil-modified polyols, castor oil derivatives etc. which have been known as polyols for polyurethane and which have in the molecule at least one of a tertiary amino group, a quaternary ammonium group and a carboxylate salt group.
  • These polyols may further contain active hydrogen such as carboxyl, amino or thiol.
  • the tertiary amino group, quaternary ammonium group or carboxylate salt group may be introduced during or after preparation of polyols by known method.
  • polyester polyols are reaction products of polyhydric alcohols and polybasic acids.
  • polyhydric alcohols mention may be made of ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polyoxypropylene glycol, polyoxybutylene glycol, glycerol, trimethylolpropane, pentaerythritol and sorbitol.
  • polybasic acids mention may be made of succinic acid, adipic acid, azelaic acid, sebacic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, maleic acid, fumaric acid and anhydrides thereof.
  • polyester polyols obtained by ring opening polymerization of lactones such as caprolactone or methylcaprolactone, with glycols.
  • polyether polyols examples are those which are obtained by addition of epoxide compounds such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, epichlorohydrin, phenylglycidyl ether and allylglycidyl ether, alone or as a mixture or alternately to active hydrogen atom-containing initiators.
  • active hydrogen atom-containing initiators mention may be made of water, polyols such as ethylene glycol, propylene glycol, glycerol, trimethylolpropane, pentaerythritol and sorbitol.
  • polyether-ester polyols mention may be made of those which are obtained by subjecting said polyether polyols and polybasic acids to esterification reaction and also, those which have both the segments of polyether and polyester in one molecule and which are obtained by ring-opening copolymerization of epoxide compounds and acid anhydrides.
  • polyester-amide polyols are those which are obtained by said polyesterification reaction where amino group-containing starting materials such as ethylenediamine, propylenediamine, hexamethylenediamine, xylylenediamine, hydrogenated xylylenediamine, ethanolamine, propanolamine are additionally used.
  • amino group-containing starting materials such as ethylenediamine, propylenediamine, hexamethylenediamine, xylylenediamine, hydrogenated xylylenediamine, ethanolamine, propanolamine are additionally used.
  • the acrylic polyols can be prepared by copolymerizing polymerizable monomers containing at least one hydroxyl group in the molecule with other monomers copolymerizable with said monomers.
  • hydroxyl group-containing monomers mention may be made of hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate, trimethylolpropane monoacrylate, their corresponding methacrylic acid derivatives, hydroxyalkyl maleates and fumarates.
  • copolymerizable monomers mention may be made of, for example, acrylic acid, its methyl, ethyl, propyl, butyl and 2-ethylhexyl esters, methacrylic acid, maleic acid, fumaric acid and itaconic acid and their esters as enumerated above and vinyl monomers such as styrene, a-methylstyrene, vinyl acetate, acrylonitrile and methacrylonitrile.
  • acrylic acid its methyl, ethyl, propyl, butyl and 2-ethylhexyl esters
  • methacrylic acid maleic acid, fumaric acid and itaconic acid and their esters
  • vinyl monomers such as styrene, a-methylstyrene, vinyl acetate, acrylonitrile and methacrylonitrile.
  • polyurethane polyols As examples of polyurethane polyols, mention may be made of reaction products of polyols and polyisocyanates which have terminal hydroxyl group.
  • the polyols are polyols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, neopentyl glycol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol and sorbitol, or polymer polyols such as polyester polyol, polyether polyol, polyester ether polyol and polyester amide polyols.
  • polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diisocyanatomethylcaproate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane, 4,4'-methylenebis(cyclohexyl isocyanate), 1,3- or 1,4-bis(isocyanatomethyl)cydohexane, methylcyclohexane-2,4-diisocyanate, m- or p-phenylene diisocyanate, diphenyimethane-4,4'-diisocyanate, 2,4- or 2,6-tolylene diisocyanate, 1,3- or 1,4-xylene diisocyanate or dimers or trimers of these polyisocyanates.
  • polyisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, 2,6-diiso
  • reaction products of said polyisocyanates with said polyols a part of which is substituted with an amino compound such as ethylenediamine, propylenediamine, hexamethylenediamine, xylylenediamine, bisaminomethylcyclo- hexane, 3-aminomethyl-3,5,5-trimethylcyclohexylamine, ethanolamine or propanolamine, may also be used as the polyurethane polyols.
  • epoxypolyols examples include epoxy resins obtained by condensation reaction of a polyphenol compound or its ring hydrogenated product with epichlorohydrin. Besides these resins, epoxy ester resins obtained by reacting a fatty acid with an epoxy resin or modified epoxy resins obtained by reacting an alkanolamine with an epoxy resin may also be used.
  • the tertiary amino group may be introduced into said polyol component, for example, by addition reaction of an epoxy compound with a primary amine, secondary amine or hydroxy compound having amino group (e.g., butylamine, ethylenediamine, diethanolamine or N-methyldiethanolamine). Therefore, in the case of the polyether polyol and polyether-ester polyol, the tertiary amino group may be introduced by using a primary amine, secondary amine or hydroxy compound having amino group as a part or the whole of the reaction initiator.
  • an epoxy compound with a primary amine, secondary amine or hydroxy compound having amino group (e.g., butylamine, ethylenediamine, diethanolamine or N-methyldiethanolamine). Therefore, in the case of the polyether polyol and polyether-ester polyol, the tertiary amino group may be introduced by using a primary amine, secondary amine or hydroxy compound having amino group as a part or the whole of the reaction initiator.
  • the tertiary amino group may be introduced by using a hydroxy compound having tertiary amino group (e.g., N,N'-dimethylethanolamine, N-methyldiethanolamine or triethanolamine) as a part or the whole of the starting polyhydric alcohol, polyether polyol or amine.
  • a hydroxy compound having tertiary amino group e.g., N,N'-dimethylethanolamine, N-methyldiethanolamine or triethanolamine
  • the tertiary amino group may be introduced by copolymerizing a vinyl monomer having tertiary amino group (e.g., dimethylaminopropyl acrylamide, morpholinoethyl methacrylate or 2-vinylpyridine), with other monomers.
  • a vinyl monomer having tertiary amino group e.g., dimethylaminopropyl acrylamide, morpholinoethyl methacrylate or 2-vinylpyridine
  • the tertiary amino group in these polyols may be present in the form of a salt with an acid component in the polyol or with other acid components.
  • the quaternary ammonium group includes a quaternary ammonium hydroxide group and a group in the form of its weak acid salt.
  • the quaternary ammonium hydroxide group may be introduced into the polyols, for example, by reacting a tertiary amino group with a halogenated hydrocarbon (e.g., alkyl halides such as methyl chloride) by known method and treating the reaction product with silver oxide, alkali hydroxides, etc.
  • a weak acid salt of quaternary ammonium e.g., CH 3 COO-
  • CH 3 COO- may be introduced by treating said product with a weak acid.
  • polyols having quaternary ammonium group may be obtained by using a hydroxy compound having quaternary ammonium group (e.g., choline salt, etc.) as a part of the starting materials used for production of said various polyols.
  • the carboxylate salt group means a carboxyl group which is in the form of a salt with alkali metals, alkaline earth metals or tertiary amino compounds.
  • they can be obtained by reacting, e.g., calcium oxide, potassium hydroxide, N-methyldiethanolamine, triethylamine, etc. with the above enumerated polyols having carboxyl group.
  • a carboxylate salt group can be introduced by using a carboxylic acid salt or a hydroxy compound having carboxylic acid salt (e.g., monosodium adipate, triethylammonium acrylate or potassium glycerate) in preparing the polyols.
  • carboxylic acid salt or a hydroxy compound having carboxylic acid salt e.g., monosodium adipate, triethylammonium acrylate or potassium glycerate
  • Said polyol component may be used alone, but may also be used in combination with compounds having active hydrogen conventionally used for polyurethanes.
  • the amount of the tertiary amino group, the quaternary ammonium group and/or the carboxylate salt group in the molecule of the polyol component is such that the proportion of nitrogen of the tertiary amino or quaternary ammonium group or that of carbonyloxy group of the carboxylate salt group to the whole composition is 0.0001 to 10% by weight, especially 0.0005 to 5% by weight.
  • the proportion of the isocyanate component having oxadiazinetrione ring to the polyol component is such that the ratio of the total number of isocyanate group and oxadiazinetrione ring to the number of hydroxyl group of the polyol component is generally in the range of 0.1 to 10, more preferably 0.5 to 3.
  • the ratio is usually in the range of 0.4 to 2, preferably 0.6 to 1.4.
  • Said polyols having at least one of a tertiary amino group, a quaternary ammonium group and a carboxylate salt group accelerate the reaction of the isocyanate component having oxadiazinetrione ring with hydroxyl group and give especially excellent curability at ambient temperature at which polyols having no said functional groups hardly cure. Further superior cured products are obtained by somewhat heating the composition. Furthermore, the cured products are also superior in weathering resistance, gloss, water resistance, solvent resistance and adhesiveness.
  • the catalyst component for the allophanate-forming reaction is incorporated into the polyol component in place of separately adding a low-molecular weight catalyst.
  • the present invention has an advantage of giving a resin onto the surface of which the catalyst does not bleed out and this does not cause undesirable changes in surface properties of the resin and deterioration thereof.
  • the polyols having a tertiary amino group, a quaternary ammonium group or a carboxylate salt group but for adjusting the reactivity of NCO group in the curing agent, it is effective to add known compounds for adjusting reaction rate of NCO group with OH group such as organic compounds, organic acid salts, or inorganic salts of tin, lead, nickel, zinc, titanium, antimony, iron, cobalt, bismuth, uranium, cadmium, aluminium, vanadium, mercury, potassium, sodium, zirconium and other metals and tertiary amines.
  • compositions of this invention are generally used as so-called two-package type compositions which comprise isocyanate component having oxadiazinetrione ring for one package and polyol component for another.
  • each component is mixed with each other as it is or in the form of solutions and the mixture is applied to the surface to be coated or adhered or injected into a mold, which cures at ambient temperature.
  • the composition of this invention is useful for coating and adhesion of woods, metals such as iron, aluminium, etc., plastics, rubber, papers, roofing tiles, concretes, etc.
  • the composition of this invention may be used in a smaller amount of curing agents than the conventional urethane curing agents, i.e., about 1/3-3/4 of the latter.
  • the composition can be used as solventless type or high solid type coating materials, adhesives, elastomers, etc.
  • a polyol component having a molecular weight of not more than 10,000 is used as a main component, the composition is for solventless type coating materials, adhesives and elastomers.
  • the pot life after mixing the components is relatively long, the mixture shows good curability. Especially when the mixture is heated (60 to 100°C for 3 to 60 minutes), practically excellent cured products can be obtained.
  • the obtained coatings have good appearance such as gloss, smoothness, etc. and excellent weathering resistance and elastomers are excellent in mechanical properties, weathering resistance, adhesiveness and wear resistance.
  • polyester polyol which was prepared from trimethylolpropane, phthalic anhydride and lauric acid, had an acid value of 4 mg KOH/g and an OH value of 140 and was as 75% butyl acetate solution
  • a polyester polyol which was prepared from trimethylolpropane, phthalic anhydride and lauric acid, had an acid value of 4 mg KOH/g and an OH value of 140 and was as 75% butyl acetate solution
  • acrylic polyol A which was prepared from styrene, methyl methacrylate, hydroxyethyl acrylate, ethyl acrylate and butyl acrylate and had an average molecular weight of 14,000, an OH value of 40 and a non-volatile matter of 50%
  • acrylic polyol B which was prepared from said monomer composition to which 1.0% of dimethylaminopropylacrylamide was added and had the same average molecular weight, OH value and non-volatile matter as the acrylic polyol A
  • isocyanate component having oxadiazinetrione ring obtained in Reference Example 1 and 2 mg of dibutyltin dilaurate.
  • each of the resultant solutions was diluted with a mixed solvent (1:1:1) of toluene, butyl acetate and 2-ethoxyethyl acetate.
  • a mixed solvent (1:1:1) of toluene, butyl acetate and 2-ethoxyethyl acetate was sprayed on a cold-rolled steel panel to form a coating of about 40 pm thickness. These panels were allowed to stand at room temperature for 7 days and properties of the coating are shown in Table 2.
  • this composition was coated to a polyester film (PET, 12 ⁇ m thick) at an amount of 1.5 g/m 2 and an aluminium foil (Al, 9 ⁇ m thick) was laminated thereon by a solventless type laminator. Then, 1.5 g/cm 2 of the composition was applied to the aluminium surface. And, a cast polypropylene film (CPP, 60 ⁇ m thick, the surface was subjected to corona discharge treatment) was laminated thereon to form three layers, which were cured at 40°C for 3 days. Adhesive strength between Al/CPP was measured to indicate 850 g/15 mm (pulling rate 300 mm/min, T-peel).
  • a bag was made from this laminate film, the inner side of which was the propylene film, and meat sauce (manufactured by Nisshin Flour Milling Co., Ltd.) was packed in this bag.
  • This sample was sterilized with hot water at 120°C for 30 minutes under a pressure of 2 kg/cm 2 and thereafter the state of adhesion and adhesive strength between Al/CPP were examined.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • General Health & Medical Sciences (AREA)
  • Physical Education & Sports Medicine (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)
  • Adhesives Or Adhesive Processes (AREA)
EP82111619A 1981-12-23 1982-12-14 Novel composition for polyurethane resins Expired EP0085776B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP56208434A JPS58109528A (ja) 1981-12-23 1981-12-23 ポリウレタン樹脂用組成物
JP208434/81 1981-12-23

Publications (2)

Publication Number Publication Date
EP0085776A1 EP0085776A1 (en) 1983-08-17
EP0085776B1 true EP0085776B1 (en) 1987-03-04

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EP82111619A Expired EP0085776B1 (en) 1981-12-23 1982-12-14 Novel composition for polyurethane resins

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US (1) US4456744A (enrdf_load_stackoverflow)
EP (1) EP0085776B1 (enrdf_load_stackoverflow)
JP (1) JPS58109528A (enrdf_load_stackoverflow)
KR (1) KR840002860A (enrdf_load_stackoverflow)
CA (1) CA1185741A (enrdf_load_stackoverflow)
DE (1) DE3275550D1 (enrdf_load_stackoverflow)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3322829A1 (de) * 1983-06-24 1985-01-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von ueberzuegen
DE3322830A1 (de) * 1983-06-24 1985-01-03 Basf Ag, 6700 Ludwigshafen Verfahren zur herstellung von ueberzuegen
US4560728A (en) * 1983-09-30 1985-12-24 Desoto, Inc. Thermally cured topcoats on vacuum deposited metal
JPS60110716A (ja) * 1983-11-18 1985-06-17 Takeda Chem Ind Ltd ポリウレタン樹脂の製造法
JPS60115615A (ja) * 1983-11-25 1985-06-22 Takeda Chem Ind Ltd ポリウレタン化合物の硬化方法
JPS6230160A (ja) * 1985-07-31 1987-02-09 Nippon Paint Co Ltd 二液型ウレタン塗料
JP3363355B2 (ja) * 1997-07-30 2003-01-08 三洋化成工業株式会社 二液型ドライラミネート用接着剤組成物
WO2002029179A1 (en) * 2000-10-02 2002-04-11 Panda Products, Inc. Adhesive materials for flooring and methods of using same
US6521298B1 (en) 2001-03-12 2003-02-18 Isotec International, Inc. Process for applying polyurethane to a substrate
JPWO2002077054A1 (ja) * 2001-03-21 2004-07-15 三井化学株式会社 オキサジアジン環を有する末端封止イソシアネートプレポリマー、その製造方法、および表面被覆材用組成物
CN1314771C (zh) * 2002-07-26 2007-05-09 三井武田化学株式会社 粘合剂组合物及软包装材料用复合薄膜
DE10246512A1 (de) * 2002-10-04 2004-04-15 Bayer Ag Niedrigviskose strahlenhärtende und thermisch härtende Polyisocyanate
US7333876B2 (en) * 2005-03-01 2008-02-19 Isotec International, Inc, Systems and methods for providing electronic quality control in a process for applying a polyurethane to a substrate
WO2014023751A1 (en) * 2012-08-10 2014-02-13 Akzo Nobel Coatings International B.V. Polyester polyol
CN110423532A (zh) * 2019-06-21 2019-11-08 王玉琢 一种高粘结性水力机械复合涂料的制备方法
US11732083B2 (en) 2020-11-19 2023-08-22 Covestro Llc Polyisocyanate resins
CN118930788B (zh) * 2024-08-13 2025-05-06 临沂斯科瑞聚氨酯材料有限公司 一种端氨基季铵盐聚合物材料的制备方法和应用

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Publication number Priority date Publication date Assignee Title
AT227952B (de) * 1960-05-25 1963-06-25 Bayer Ag Verfahren zur Herstellung von Schaumstoffen auf Isocyanatbasis
CA932333A (en) * 1966-02-02 1973-08-21 Farbenfabriken Bayer Aktiengesellschaft Compounds containing the 2,4,6-triketo-1,3,5-oxadiazine ring
US3748329A (en) * 1970-07-08 1973-07-24 Bayer Ag Compounds containing the 2,4,6-triketo-1,3,5-oxadiazine ring
JPS493000B1 (enrdf_load_stackoverflow) * 1970-12-28 1974-01-23
JPS579773A (en) * 1980-06-23 1982-01-19 Takeda Chem Ind Ltd Production of polyisocyanate

Also Published As

Publication number Publication date
EP0085776A1 (en) 1983-08-17
KR840002860A (ko) 1984-07-21
CA1185741A (en) 1985-04-16
US4456744A (en) 1984-06-26
DE3275550D1 (en) 1987-04-09
JPH028614B2 (enrdf_load_stackoverflow) 1990-02-26
JPS58109528A (ja) 1983-06-29

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